WO2021189083A1 - Anode à base de métal lithium à haute densité d'énergie pour batteries lithium-ion à l'état solide - Google Patents

Anode à base de métal lithium à haute densité d'énergie pour batteries lithium-ion à l'état solide Download PDF

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Publication number
WO2021189083A1
WO2021189083A1 PCT/US2021/070290 US2021070290W WO2021189083A1 WO 2021189083 A1 WO2021189083 A1 WO 2021189083A1 US 2021070290 W US2021070290 W US 2021070290W WO 2021189083 A1 WO2021189083 A1 WO 2021189083A1
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solid
lithium
battery
anode
state
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PCT/US2021/070290
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English (en)
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Claudiu B. Bucur
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Piersica Inc.
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Priority to EP21770847.8A priority Critical patent/EP4122032A1/fr
Priority to CN202180022486.7A priority patent/CN115315832A/zh
Priority to CA3171696A priority patent/CA3171696A1/fr
Priority to MX2022011419A priority patent/MX2022011419A/es
Priority to KR1020227035613A priority patent/KR20220156571A/ko
Priority to JP2022555782A priority patent/JP2023518060A/ja
Publication of WO2021189083A1 publication Critical patent/WO2021189083A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H01M4/806—Nonwoven fibrous fabric containing only fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/137—Electrodes based on electro-active polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/664—Ceramic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the instant disclosure relates to chemistry, namely electrical current producing apparatuses. More particularly, the instant disclosure relates to the manufacture of battery components having certain improvements to the manufacture of an anode in order to increase performance, safety, and reliability of the overall battery.
  • a lithium-ion battery or Li-ion battery, is a type of rechargeable battery commonly used in portable electronics and electric vehicles. Compared with previous battery technologies, lithium-ion batteries offer faster charging, larger capacity, and higher power density which allows for greater performance in a smaller and lighter package. While there are a large number of reasons that lithium has become a favorable element in battery technology, the most important reasons have to do with its elemental structure. Lithium is highly reactive because it readily loses its outermost electron, allowing current to easily flow through a battery. As the lightest metal, lithium is much lighter than the other metals commonly used in batteries (e.g., lead). This property is important for small objects such as phones but also for cars that require many batteries.
  • lithium-ions and electrons move easily back into positive electrodes (cathodes), allowing for numerous recharging cycles.
  • Innovation in lithium-ion battery technology has helped to minimize the form factor of electronic devices while simultaneously increasing their capabilities. Smart phones, smart watches, wearable devices, and other modem electronic luxuries simply would not be possible without some of the lithium-ion battery advances witnessed in recent decades.
  • lithium-ion batteries use a liquid electrolyte.
  • the liquid electrolytic solution in a liquid electrolyte lithium-ion battery is used to regulate the current flow during charging and discharging.
  • Current “flows” through the liquid electrolytic solution between the anode and cathode in order to allow a battery user to store and then use the electrical energy stored with the battery.
  • lithium-ions move from the negative electrode (the anode) through an electrolyte to the positive electrode (the cathode) during discharge, and back when charging.
  • These lithium-ion batteries usually use an intercalated lithium compound as the material at the cathode and graphite at the anode.
  • LiC 6 Graphite in its fully lithiated state of LiC 6 correlates to a maximal capacity of 372 mAh/g.
  • liquid lithium-ion batteries While liquid lithium-ion batteries have a high energy density, no memory effect, and low self-discharge, they can be a safety hazard since they contain flammable electrolytes. If damaged and exposed to air or incorrectly charged, these batteries can lead to or even cause explosions and fires. Removable lithium-ion battery recalls due to fire hazard are common and costly, and several portable electronics manufacturers have even been forced to recall expensive electronic devices without removable batteries due to lithium-ion fires. This issue is of increasing concern due to incorporation of liquid lithium-ion batteries in electric vehicles (EVs).
  • EVs electric vehicles
  • an EV liquid lithium-ion battery may be readily ignited when exposed to water in the air, thus posing a major safety problem.
  • This safety issue is becoming more important to address as electric vehicles become increasingly commercially viable and more widely adopted.
  • Lithium in its solid-state has a maximum possible capacity of 3600 mAh/g, or nearly ten times that off LiC 6 .
  • lithium metal is also highly reactive in its solid-state and it plates very unevenly.
  • the present disclosure overcomes the above-mentioned disadvantages and meets the recognized need for such an anode by introducing various improvements to the manufacture, construction, and design of batteries to accommodate a lithium-ion anode having a solid electrolyte (i.e., a solid-state lithium-ion anode).
  • a lithium-ion anode having a solid electrolyte i.e., a solid-state lithium-ion anode.
  • These generally include but are not limited to a lithium-ion conductor, an electronic conductor, mixed ionic/electronic conductors, lithophilic coatings, current collector(s), and improved welds, either separately or in combination.
  • these improvements have the potential to increase the energy storage capacity of a lithium-ion battery from its theoretical maximum in liquid electrolyte form to its more energy dense solid form. Additionally, these improvements, alone and/or in combination, help to decrease the potential for harm, such as fire, resulting from expansion, swelling, or damage to a lithium-ion battery. These improvements, alone and/or in combination, may allow for these benefits without the sacrifice of decreasing charging speed and power supply to devices.
  • One aspect of the high energy density lithium metal based anode for solid-state lithium-ion batteries may be a lithium-ion conductor.
  • the lithium-ion conductor may be manufactured in a variety of forms, each having corresponding benefits and tradeoffs. These variations in forms may be better understood to be separate distinct embodiments of the lithium-ion conductor.
  • the lithium-ion conductor may be comprised of a ceramic framework.
  • the ceramic framework, or skeleton may be utilized to support the lithium metal of the lithium-ion conductor.
  • Lithium metal may provide the electronic conductivity while the solid ceramic framework/skeleton may provide volumetric support and lithium-ion conductivity.
  • One means to combine and/or operably engage lithium metal with the ceramic framework/skeleton may be through melt infusion of lithium metal into a treated ceramic framework. Initially, only a smally quantity of lithium metal may be needed to be infused into the pre-cell assembly.
  • all reversible lithium which gives a cell its capacity may instead come from the cathode in the final assembly.
  • cathodes such as lithium ferrophosphate (LFP), lithium cobalt oxide (LCO), nickel/manganese/cobalt (NMC), the like and/or combinations thereof varieties of cathodes.
  • LFP lithium ferrophosphate
  • LCO lithium cobalt oxide
  • NMC nickel/manganese/cobalt
  • the higher surface area of the ceramic skeleton may allow for higher rates of operation (plating/stripping of lithium) of the solid battery if compared to a flat lithium foil. From the point of view of energy density, an important requirement for ceramic skeletons may be the use of low-density ceramic.
  • a proposed example low-density lightweight ceramic may be Lii +X Al x Ti2- x P3O12 (LATP).
  • Lii +X Al x Ti2- x P3O12 LATP
  • additional components, methods of manufacture, and further variation that include various benefits and tradeoffs. These may include choice in active material and type of functional material processing.
  • a polymer framework or skeleton may be preferred.
  • a polymer skeleton/framework of the lithium conductor aspect of the high energy density lithium metal based anode for solid-state lithium-ion batteries may offer the added benefit of being flexible, where a ceramic framework/skeleton may be described as rigid.
  • Requirements of a polymer framework/skeleton may be (a) having a melting point above the melting point of lithium metal (180C), (b) high conductivity of lithium-ions, and (c) infusion with lithium conductive material into the structure, such as other conductive polymers with the corresponding lithium salt (e.g., Lithium bis(trifluoromethanesulfonyl)imide / L C F NO S / LiTFSI) or ceramic particles imbedded into the polymer and/or upon its surface.
  • lithium conductive material such as other conductive polymers with the corresponding lithium salt (e.g., Lithium bis(trifluoromethanesulfonyl)imide / L C F NO S / LiTFSI) or ceramic particles imbedded into the polymer and/or upon its surface.
  • lithium salt e.g., Lithium bis(trifluoromethanesulfonyl)imide / L C F NO S / LiTFSI
  • ceramic particles im
  • a hybrid composite framework or skeleton may be preferred.
  • the lithium-ion conductor having a hybrid composite framework/skeleton there may be components, methods of manufacture, and further variation that include various benefits and tradeoffs. These may include a fiber mat which may further include fumed silica and G4/LiTFSA, boron nitride/vanadium nitride doping, doping of other nitrides, the like and/or combinations thereof.
  • Another aspect of the high energy density lithium metal based anode for solid-state lithium-ion batteries is an electronic conductor.
  • an electronic conductive component may be required in the anode to improve electronic conductivity and homogeneous plating during charging. These materials may also play a crucial role in inhibiting dendritic growth of lithium. Eutectic mixtures of lithium with other metals may provide a softer lithium based metal anode having properties of plastic flow.
  • Yet another aspect of the high energy density lithium metal based anode for solid- state lithium-ion batteries may be the incorporation of mixed ionic/electronic conductors (MIEC) at the battery electrode.
  • MIEC mixed ionic/electronic conductors
  • MIECs may be a very promising class of materials for solid electrodes. MIECs differ from solid ionic conductors in that they conduct electrons themselves, in addition to ions. MEICs may be best suited for electrodes, where both electronic and ionic conduction may be required. MEICs may be incapable of use as battery separators, where only ionic conductivity (and electronic insulation) may be required.
  • Yet another aspect of the high energy density lithium metal based anode for solid- state lithium-ion batteries may be lithiophilic coatings to either a ceramic and/or polymer framework/skeleton.
  • Lithiophilic coatings may be crucial for the use of ceramic or polymeric skeletons. Since ceramic and/or polymer frameworks/skeletons may not have a good interface with lithium metal in their unimproved state, an improvement incorporating coatings having lithiophilic properties may be critical to the inclusion of these types of frameworks/skeletons in a high energy density lithium metal based anode for solid-state lithium-ion batteries.
  • lithiophilic coatings may further encourage reduction of dendritic growth of lithium during plating and/or promote smooth plating.
  • Lithiophilic coatings of ceramic and/or polymer frameworks/skeletons may also extend the range of suitable choices for ceramic or polymeric frameworks/skeletons to materials which may otherwise react with lithium absent the lithiophilic coatings, thereby which may otherwise prevent certain ceramics and/or polymers from being used in conjunction with lithium in a coating-free state.
  • Lithiophilic coatings come in a variety of forms, each of which may involve their own protocol for distribution and adherence to a surface of a ceramic and/or polymer framework/coating.
  • the high energy density lithium metal based anode may be understood, either by virtue of lithiophilc properties of the materials used to create a lithiophilic framework, or through the addition of lithiophilic coating(s), to be a fiber mat or polymer mat having lithiophilic properties, the fiber mat or polymer fiber mat having one or more cavities by which lithium or other metals may be deposited.
  • Yet another aspect of the high energy density lithium metal based anode for solid- state lithium-ion batteries may be a current collector for the anode.
  • a current collector is an electronic conductor which carries the electrons from the anode to the cathode through an external load, powering the load device.
  • copper foil is used for anode current collectors. Use of copper foil further provides support for commercial graphite anodes.
  • the development of a new type of current collector which bonds well with the ceramic and/or polymer framework/skeleton having infused lithium metal may be required in the high energy density lithium metal based anode for solid-state lithium-ion batteries may be a current collector for the anode of the disclosure to carry the electrons through the load during charging and operation of the batteries.
  • Yet another aspect of the high energy density lithium metal based anode for solid- state lithium-ion batteries may be a novel method of fusion among the high energy density lithium metal based anode for solid-state lithium-ion batteries, its coatings and components, and the surrounding battery components.
  • Copper current collectors may be typically weld tabbed together in order to carry electronic current to bus bars outside the battery cells.
  • development of weld tabbing the current collector as described herein to a ceramic and/or polymer framework/skeleton having lithiophilic coatings and in combination with solid lithium metal may further enhance, or even make possible, the high energy density lithium metal based anode for solid-state lithium-ion batteries of the disclosure.
  • various aspects and features of the high energy density lithium metal based anode for solid-state lithium-ion batteries may offer benefits over both traditional liquid electrolyte lithium-ion batteries, as well as over existing, available, experimental, and/or proposed solid-state lithium-ion batteries.
  • a benefit of the high energy density lithium metal based anode for solid-state lithium-ion batteries may be its ability to increase the energy density of anodes above that of currently commercial graphite based anodes.
  • Another benefit of the high energy density lithium metal based anode for solid-state lithium-ion batteries may be its ability to provide high currents of operation above the currently observed 0.1-0.5 mA/cm 2 for solid-state batteries and nearing as high as 10 mA/cm 2 which may be of significant commercial significance for charging a battery in less than 30 minutes.
  • Another feature of the high energy density lithium metal based anode for solid-state lithium-ion batteries may be its ability to provide a safe lithium metal anode structure with lithiophilic interphases which may result in high cycle life (e.g., greater than 4000 cycles), which may also be of commercial significance for electric vehicles and other durable goods requiring longevity of installed batteries.
  • Another feature of the high energy density lithium metal based anode for solid-state lithium-ion batteries may be the ability to operate over a much wider temperature range (e.g., -60°C to 150°C) than even currently available commercial graphite based anodes (-30°C to 60°C).
  • Another feature of the high energy density lithium metal based anode for solid-state lithium-ion batteries may be the ability to provide a pre-lithiated anode during manufacture.
  • Another feature of the high energy density lithium metal based anode for solid-state lithium-ion batteries may be the ability to provide a flexible anode.
  • Another feature of the high energy density lithium metal based anode for solid-state lithium-ion batteries may be the ability to pass a nail penetration test which commercial graphite based anodes cannot do.
  • Another feature of the high energy density lithium metal based anode for solid-state lithium-ion batteries may be the ability of the anode to resist combustion because, for instance, due to high ceramic content of possibly preferred embodiments of the high energy density lithium metal based anode for solid-state lithium-ion batteries, few flammable components would exist in the batteries of the disclosure.
  • Another feature of the high energy density lithium metal based anode for solid-state lithium-ion batteries may be the various scalable processes resulting a mass produce-able lithium based anode.
  • FIG. 1 is a perspective view of a section of an exemplary embodiment of the high energy density lithium metal based anode for solid-state lithium-ion battery of the disclosure.
  • FIG. 2 is a diagram of components of a prior art battery.
  • FIG. 3 is a block drawing of a battery.
  • FIG. 4 is a flow chart of an exemplary method of manufacture of the high energy density lithium metal based anode of the disclosure.
  • battery cell, anode, cathode and separator, in their singular and plural form, are used as they relate to the high energy density lithium metal based anode for solid-state lithium-ion batteries of the disclosure, as well as used to describe other batteries, including but not limited to lithium-ion batteries having a liquid electrolyte.
  • a single cell of a battery may be herein described, one skilled in the art of battery manufacture will understand that multiple cells may be used in the design, construction, manufacture, and assembly of a battery, and multiple batteries may be arranged and/or installed within a completed manufactured good.
  • fiber framework is used consistently throughout this detailed description, it may also be understood as a fibrous battery skeleton.
  • FIGS. 1-4 by way of example, and not limitation, therein are illustrated example embodiments of high energy density lithium solid-state anode 111 for solid-state battery 100.
  • Solid-state lithium-ion battery 100, liquid electrolyte battery 200, and battery 300 may be referred herein as just the battery.
  • High energy density lithium metal based solid-state anode 111, liquid electrolyte anode 211, and anode 311 may be referred herein as just the anode. While variations in construction, design, composition, chemistry, and assembly may be relevant to cathode 312, for the sake of clarity and consistency across FIGS.
  • any reference to cathode 312 is simply the cathode, and other relevant features may be referred to in a description as it relates to solid-state battery 100, liquid electrolyte battery 200, and battery 300.
  • Solid separator 131, porous separator 231, and solid separator 131 may be referred herein as just the separator.
  • Solid-state battery 100, liquid electrolyte battery 200, and battery 300 may be charged via charger 351 and may discharge into device 352.
  • solid-state battery 100, liquid electrolyte battery 200, and battery 300 may each have a single cell or may have multiple cells connected and/or assembled in multiple layers of anode 311, cathode 312, and separator 331.
  • Lithium, lithium metal, elemental lithium, and lithium-ions may be referred to interchangeably herein, and the disclosure is not so limited to a battery having lithium metal as its electrical flow element.
  • Other elements may include but are not limited to zinc, sodium, cobalt, nickel, lead, potassium, other metals, salts thereof, the like and/or combinations thereof.
  • solid-state battery 100 may include the following components: solid-state anode 111 having solid electrolyte 112 with fiber framework and shown with metal ion deposit 120, solid separator 131, and cathode 312 having solid-state cathode current collector 132.
  • liquid electrolyte lithium-ion battery 200 may include the following components: liquid electrolyte anode 211 having graphite anode active material 212 and anode current collector 233, porous separator 231, and cathode 312 having liquid electrolyte cathode current collector 232.
  • battery 300 may include the following components and connections: anode 311, cathode 312, separator 331, charger 351, and powered device 352.
  • Solid-state anode 111 having solid separator 131 both above and beneath solid-state anode 111.
  • Solid-state anode 111 may be formed from one or more layers of solid electrolyte 112, of which each layer of solid electrolyte 112 may be formed from a fiber framework.
  • solid-state anode 11 may be understood as the negative or reducing electrode that releases electrons to the external circuit (see FIG. 3) and oxidizes during an electrochemical reaction.
  • the cathode 312 may be understood as the positive or oxidizing electrode that acquires electrons from the external circuit (see FIG. 3) and is reduced during the electrochemical reaction.
  • solid-state anode 111 may be comprised solid electrolyte 112, which can be understood as a framework of interconnected fibers.
  • the framework interconnected fibers therein solid-state anode 111 may have a variety of properties and may be either flexible or rigid.
  • ceramic may be utilized to provide structure, support to solid- state anode 111 and solid-state battery 100, as well as a surface upon which lithium, or other metals, may deposit.
  • Lithium metal at metal ion deposit 120 may provide the electronic conductivity for solid-state battery 100 while the solid ceramic framework/skeleton may provide volumetric support, surface layer for metal ion deposit 120 and lithium-ion conductivity.
  • metal ion deposit 120 may grow in size toward solid separator 131 or shrink toward center of solid-state anode 111.
  • One means to combine, manufacture, and/or operably engage metal ion deposit 120 with the fiber framework of solid electrolyte 112 may be through the melt infusion of lithium metal into a treated ceramic framework. Initially, only a smally quantity of lithium metal may be needed to be infused into the pre-cell assembly of solid-state anode 111. In such a case where only a small quantity is infused into the pre-cell assembly of solid-state anode 111, most or even all reversible lithium which gives a cell its capacity may instead come from cathode 312 in the final assembly.
  • metal ion deposit 120 may be detected or observed to be very small at or approximate the center of solid-state anode 111.
  • metal ion deposit 120 may be detected or observed to grow in size outward toward solid separator 131, even growing to occupy all space within the fiber framework of solid-state anode 111 along solid electrolyte 112.
  • the deposit of lithium and/or other metals may further occur through temporary use of high voltage insertion cathodes such as lithium ferrophosphate (LFP), lithium cobalt oxide (LCO), nickel/manganese/cobalt (NMC), the like and/or combinations thereof varieties of cathodes.
  • LFP lithium ferrophosphate
  • LCO lithium cobalt oxide
  • NMC nickel/manganese/cobalt
  • the higher surface area of solid electrolyte 112 having a ceramic fiber framework may allow for higher rates of operation (plating/stripping of lithium) of solid-state battery 100 if compared to a flat lithium foil.
  • a flat lithium foil may also be used as an initial form of metal ion deposit 120 and may also be melt infused along center of solid-state anode 111 within solid electrolyte 112.
  • an important requirement for ceramic fiber frameworks of solid electrolyte 112 may be the use of low-density ceramic.
  • a proposed example low-density lightweight ceramic may be Lii +X Al x Ti 2 x P 3 O 12 (LATP).
  • solid-state anode 111 having solid electrolyte 112 comprising ceramic
  • additional components, methods of manufacture, and further variation that include various benefits and tradeoffs. These may include choice in active material and type of functional material processing.
  • coating materials having qualities which attract particular metals may provide increased benefits to encourage smooth, consistent plating along the internal fiber framework.
  • These may include engineering solid-state anode 111 having solid electrolyte 112 to measure approximately 80-90pm in total per-layer thickness, approximately 5cm X 5cm total length and width along solid separator 131, with porosity of internal fiber framework of percentages greater than 70%, having individual and/or average fiber diameters of less than 0.35pm, having individual and/or average fiber lengths of greater than 1mm, having a coating thickness of approximately lOnm, and having coating material comprising oxides, nitrides, polymers, or ceramics.
  • Oxide coating materials for fibers within solid electrolyte 112 include niobum, AI 2 O 3 + ZnO (AZO), aluminum, indium, zinc, bismuth, magnesium, silicon, gold, iodine, and sulfur oxides, the like and/or combinations thereof oxides.
  • Nitride coating materials for fibers within solid electrolyte 112, by way of example and not limitation include boron, vanadium nitrides, the like and combinations thereof.
  • Polymer coating materials for fibers within solid electrolyte 112, by way of example and not limitation include succinonitrile (SCN).
  • Ceramic coating materials for fibers within solid electrolyte 112 by way of example and not limitation include closoborates (CB), lithium phosphorus oxynitride (LiPON), the like, and/or combinations thereof.
  • CB closoborates
  • LiPON lithium phosphorus oxynitride
  • Ceramic coating materials for fibers within solid electrolyte 112 by way of example and not limitation include closoborates (CB), lithium phosphorus oxynitride (LiPON), the like, and/or combinations thereof.
  • a polymer framework in solid electrolyte 112 be preferred.
  • a polymer framework of solid electrolyte 112 within solid-state anode 111 may offer the added benefit of being flexible, where the previous ceramic fiber framework of solid electrolyte 112 within solid-state anode 111 may be described as rigid. This may offer various benefits and tradeoffs, both at the level of the individual cell or layer of solid-state battery 100, but also offer various tradeoffs and benefits to powered device 352, having there installed solid-state battery 100.
  • Requirements of a polymer framework, and materials therein deposited, of solid-state anode 111 may be (a) having a melting point above the melting point of lithium metal (180C), (b) non-conductivity of lithium-ions, and (c) infusion with lithium conductive material into the structure of solid electrolyte 112, such as other conductive polymers with the corresponding lithium salt (e.g., Lithium bis(trifluoromethanesulfonyl)imide / L1C 2 F 6 NO 4 S 2 / LiTFSI) or ceramic particles embedded into the polymer and/or upon its surface.
  • lithium salt e.g., Lithium bis(trifluoromethanesulfonyl)imide / L1C 2 F 6 NO 4 S 2 / LiTFSI
  • solid-state anode 111 having a polymer framework of solid electrolyte 112 there may be additional components, methods of manufacture, and further variation that include various benefits and tradeoffs. These may include a fiber mat which extends throughout solid-state anode 111 and solid electrolyte 112, which may further include aramids and polyimide frames. Furthermore, while not all coatings for ceramic fiber framework may be applicable to a polymer or polymer fiber framework, and while not all properties and features of a ceramic fiber framework may be directly applicable to a polymer or polymer fiber framework, some may.
  • These may include engineering solid- state anode 111 having solid electrolyte 112 to measure approximately 80-90pm in total per- layer thickness, approximately 5cm X 5cm total length and width along solid separator 131, with porosity of internal fiber framework of percentages greater than 70%, having individual and/or average fiber diameters of less than 0.35pm, having individual and/or average fiber lengths of greater than 1mm, having a coating thickness of approximately lOnm, and having coating material comprising oxides, nitrides, polymers, or ceramics.
  • Oxide coating materials for fibers within solid electrolyte 112 include niobium, AI 2 O 3 + ZnO (AZO), aluminum, indium, zinc, bismuth, magnesium, silicon, gold, iodine, and sulfur oxides, the like and/or combinations thereof oxides.
  • Nitride coating materials for fibers within solid electrolyte 112, by way of example and not limitation include boron, vanadium nitrides, the like and combinations thereof.
  • Polymer coating materials for fibers within solid electrolyte 112, by way of example and not limitation include succinonitrile (SCN).
  • Ceramic coating materials for fibers within solid electrolyte 112 by way of example and not limitation include closoborates (CB), lithium phosphorus oxynitride (LiPON), the like, and/or combinations thereof.
  • CB closoborates
  • LiPON lithium phosphorus oxynitride
  • Ceramic coating materials for fibers within solid electrolyte 112 by way of example and not limitation include closoborates (CB), lithium phosphorus oxynitride (LiPON), the like, and/or combinations thereof.
  • CB closoborates
  • LiPON lithium phosphorus oxynitride
  • ceramics which may not bind readily to lithium, or other metals may be encouraged to bind to lithium, thereby acting as an electrolyte upon which solid metals, including lithium-ions, may freely move during charge and discharge.
  • initial deposits of lithium may be important for several reasons.
  • metal ion deposit 120 may be formed initially at metal ion deposit 120 in a very small, nearly insubstantial amount, but grow in size, weight, and volume, and even may occupy all empty space within solid-state anode 111 and solid electrolyte 112. This may be accomplished through various means, though a potentially preferred process to initially deposit metal near the center of solid-state anode 111 on the surface of solid electrolyte 112, and its fibers, may be through the melt infusion of lithium foil.
  • the manufacture of the fibers themselves, whether ceramic or polymer, may offer a variety of important improvements to the structure, formation, and overall properties of solid electrolyte 112, solid-state anode 111 and solid-state battery 100.
  • These techniques may have little to no known applications in the battery technology industry, but may have significant applications in the materials sciences and non-woven material industry.
  • One such process may include sol-gel processes, which may preferably occur prior to deposit of metal ion deposit 120.
  • a "sol" a colloidal solution
  • a gel-like diphasic system containing both a liquid phase and solid phase whose morphologies range from discrete particles to continuous polymer networks.
  • the volume fraction of particles may be so low that a significant amount of fluid may be required to be removed initially for the gel-like properties to be recognized.
  • One such means of fluid removal may be to simply allow time for sedimentation to occur, and then pour off the remaining liquid. Centrifugation can also be used to accelerate the process of phase separation. Removal of the remaining liquid (solvent) phase requires a drying process and may result in a significant amount of shrinkage and densification. The rate at which the solvent can be removed is ultimately determined by the distribution of porosity in the gel.
  • the ultimate microstructure of the final component can be strongly influenced by changes imposed upon the structural template during this phase of processing.
  • a thermal treatment, or firing process is often necessary in order to favor further polycondensation and enhance mechanical properties and structural stability via final sintering, densification, and grain growth.
  • One of the distinct advantages of using this methodology as opposed to the more traditional processing techniques is that densification is often achieved at a much lower temperature.
  • the precursor sol can be either deposited on a substrate to form a film (e.g., by dip-coating, spin coating, or electrospinning), cast into a suitable container with the desired shape (e.g., to obtain monolithic ceramics, glasses, fibers, membranes, aerogels), or used to synthesize powders (e.g., microspheres, nanospheres).
  • This technique in combination with electrospinning, is known to create a paper-like material having open cavities which may be highly suitable for the depositing of metals, namely lithium ions. Additional processes which may further enhance this space-filling and open cavity feature of solid electrolyte 112, using various compositions of the disclosed ceramics and polymers, may include co-precipitation, evaporation and self-assembly, and utilization of nano-particles.
  • the material by which the fibrous structure having open cavities, the fibrous structure having a lithiophilic coating may be considered an active material, of which comprises solid-state anode 111.
  • the active material of solid-state anode 111 may be solid electrolyte 112, which is the active material through which lithium-ions migrate, congregating at metal ion deposit 120. Whichever active material is manufactured in order to create solid-state anode 111 can be processed into a functional material having these properties and acting as solid electrolyte 112 of solid-state battery 100.
  • a first stage in this process may be synthesis of a fiber mat including substances such as LATP, closoborates, and sulfide ceramics.
  • Stages in the sol-gel, or other processes to form the open cavity structure of solid electrolyte 112 may be improved through lower the firing temperature required by implementation of aliovalent substitutions.
  • Other improvements may include maximize density by using flux additives (e.g., Li 2 0, MgO, ZnO, U3PO4, U3BO3, B 2 0 3 , LiB0 2 , A1 2 0 3 , Ta, Nb, Y, Al, Si, Mg, Ca, YSZ, NiO, Fe 2 0 3 , the like, and/or combinations thereof).
  • flux additives e.g., Li 2 0, MgO, ZnO, U3PO4, U3BO3, B 2 0 3 , LiB0 2 , A1 2 0 3 , Ta, Nb, Y, Al, Si, Mg, Ca, Y
  • the active material of a pre-assembly solid electrolyte 112 may be required to obtain a rugged functional laminate, sheets or mats for use as solid-state anode 111.
  • Slurry additives may be added in order to process a green laminate during the process of rapid sintering. These slurry additives may include, but are not limited to resins, oils, and dispersants (e.g.,PAA, glucose, PVP, ethylene glycol, oleic acid, ultrasonic horn, the like and/or combinations thereof). Sintering of the green material using traditional techniques known to those skilled in the art can be a long process (>10 hours) and may need to occur at high temperatures (> 1250°C).
  • the resulting sintered green laminate should contain voids for lithium metal melt infusion, subsequent to sintering, which can then occur at room temperature.
  • Voids can instead be built in by using sacrificial plastic/carbon beads or by electrospinning the into fiber mats, as described above.
  • the resulting solid electrolyte 112 may then be suitable for deposit of lithium along metal ion deposit 120.
  • Alternative measures to encourage these properties in solid electrolyte 112, thereby creating an optimal solid-state anode 111 may include buy are not limited to reactive sintering of starting materials, sintering within an electric field, microwave sinter, SPS or spark plasma, cold sintering using solvent evaporation and salts CSP, and flash sintering using high currents.
  • porous sheets may be manufactured using sacrificial beads which are various plastics or carbons with low vaporization temperatures that can be removed and/or destroyed leaving openings in the fiber mat, or the development of a ceramic fiber mat through electrospinning.
  • polymer fiber versions of solid electrolyte 112 include the use of polymers having melting points of lithium metal (180C). These polymers, however, typically do not conduct lithium- ions so they, would serve a structural role upon which additional lithium conductive material may be infused into the structure such as other conductive polymers (with the corresponding lithium salt such as LiTFSI) or ceramic particles.
  • fiber mat comprising polyimide (having melting point of 450°C) may be used to infuse with melted lithium and serve as a coating.
  • Further examples include aramids, polyimide frames.
  • a hybrid composite fiber mat could include fumed silica and G4/LiTFSA with boron/vanadium (or other nitrides) doping upon the surface.
  • coating alternatives which may offer, either alone or in combination, additional benefits to the deposit, motility, and smooth plating of metal ion deposit 120.
  • These may include CVD/PVD/PECVD and/or ALD vapor deposition in combination with AZO coating, use of I 2 , Li 3 N, Li 3 P0 4 , LLZO, LigAlSiOg, LfiOCl, LiI: CH 3 OH, or use of metals which alloy well with lithium, including but not limited to aluminum, indium, zinc, magnesium, silicon, and/or gold.
  • Solution coating may also be used upon, or form a critical component of, solid electrolyte 112, which may be developed using a sulfur-based solution coating method with solutions of, for example, poly sulfides, dissolved sulfur ZnO doped argyrodite Li 6 PS5Br, Li 2 S 3 or Li 3 S 4 dissolved in DEGDME.
  • Polymer coatings may additionally be employed as a surface coating to solid electrolyte 112, which may include SN/FEC with additives and salts (e.g., CSPF 6 , CSTFSI, LiN0 3 , LiF, CuF 2 ), elastomers such as SHP, and even glues such as polydopamine and/or polysiloxanes.
  • solid electrolyte 112 may offer various benefits, including reduction in dendritic growth of lithium during plating at metal ion deposit 120 and on solid electrolyte 112, extending possible range of choices for solid electrolyte 112 composition for various applications, and prevention reaction between various highly useful materials for construction of solid-state anode 111 and lithium, or other, metals.
  • metal ion deposit 120 may be replaced by an anode current collector placed therein solid-state anode 111 within solid electrolyte 112. These may include foils or coatings upon which metals, specifically lithium, may be deposited.
  • Exemplary materials for an anode current collector placed therein solid-state anode 111 within solid electrolyte 112 may include but are not limited to vanadium nitride, lithium- aluminum alloy(s), liquid metals including gallium, indium, and tin, the like, and/or combinations thereof.
  • liquid electrolyte lithium-ion battery 200 may include liquid electrolyte anode 211 having graphite anode active material 212 and anode current collector 233, porous separator 231, and cathode 312 having liquid electrolyte cathode current collector 232.
  • Known variations of lithium-ion batteries having liquid electrolytes may achieve 275 Wh/kg capacities and feature the ability to recharge, but have the serious shortcomings covered in the Background section above.
  • solid-state battery 100 may achieve substantially higher capacities while allowing for additional benefits such as durability, safety, quick charging, as well as other above-mentioned benefits.
  • additional benefits such as durability, safety, quick charging, as well as other above-mentioned benefits.
  • the 275 Wh/kg capacity of liquid electrolyte lithium-ion battery 200 can be compared to solid-state battery 100 of the disclosure, which has in various forms and combinations, achieved upwards of 635 Wh/kg.
  • FIG. 3 illustrated therein is a simple block diagram for battery 300 having anode 311, cathode 312, separator 331, charger 351, and powered device 352.
  • a circuit is formed with anode 311, thereby charging battery 300.
  • a circuit is formed with anode 311 and powered device 351 is powered.
  • Each of charging and powering occur through any form of known electrochemical processes between anode 311 and cathode 312.
  • solid-state anode 111 of solid-state battery 100 the parts and features of battery 300 may be required to fully manufacture and use solid-state battery 100.
  • various improvements to the parts of battery 300 as known and developed in the art of battery manufacture, including solid-state battery 100 manufacture, may further increase the benefits as herein described of solid-state anode 111.
  • a mere substitution of solid-state anode 111 for anode 311 may not suffice, and one skilled in the art of battery design and manufacture may implement and adapt the features of solid-state anode 111 into battery 300 so as to fully take advantage of the disclosure herein.
  • FIG. 4 illustrated therein is a flowchart of an exemplary method of manufacture of solid-state anode 111 of solid-state battery 100.
  • fibrous framework is formed into solid-state anode 111, which is an active material.
  • additional layers of fibrous framework may be assembled to form solid-state anode 111 at second step (optional) 402 and the layers of fibrous framework may be fused at third step (optional) 403.
  • a lithiophilic coating may be applied to solid-state anode 111 at forth method step 404.
  • a lithium deposit may be infused into solid-state anode 111 to form metal ion deposit 120.
  • solid-state anode 111, solid separator 131, and solid-state cathode 312 may be placed in contact with each other at sixth method step 406, then tabbing welding may be used to connect solid-state anode 111 and solid-state cathode 312. Steps of the disclosed method of FIG. 4 may be reordered, repeated, and/or rearranged as one skilled in the art shall desire to achieve the intended effects.
  • the high energy density lithium metal based anode, or solid-state anode 111, for solid-state lithium-ion batteries (solid-state battery 100) and the various parts and components herein described may include a variety of overall sizes and corresponding sizes for and of various parts, including but not limited to: solid-state anode 111, solid electrolyte 112, metal ion deposit 120, solid separator 131, cathode 312, cathode current collector 132 the like and/or combinations thereof. Indeed, those various parts and components of solid-state battery 100 may vary in size, shape, etc. during the standard operation of solid-state battery 100.
  • the high energy density lithium metal based anode for solid-state lithium-ion batteries of the disclosure may have applications for powering other vehicles, computers, businesses, homes, industrial facilities, consumer and portable electronics, hospitals, factories, warehouses, government facilities, datacenters, emergency backup, aerospace, space travel, robotics, drones, the like and/or combinations thereof.
  • the chemical formulas, metals, atomic and molecular compositions are exemplary only.

Abstract

Un ensemble d'anodes solides à base de lithium est destiné à être formé en une batterie lithium-ion. Les anodes sont formées avec une structure céramique ou polymère fibreuse ayant des espaces ouverts et un matériau de surface active ayant des propriétés lithiophiles. Les espaces ouverts dans la structure fibreuse et les revêtements lithiophiles déposés sur la surface de la structure fibreuse permettent le transport libre de lithium-ions solide dans les anodes. À l'état solide, les batteries au lithium peuvent présenter une plus grande capacité par rapport au poids, une charge plus rapide, et être plus durables dans des conditions de manipulation et de température extrêmes. L'invention concerne également un procédé de fabrication d'une batterie au lithium à l'état solide munie d'une telle anode.
PCT/US2021/070290 2020-03-18 2021-03-18 Anode à base de métal lithium à haute densité d'énergie pour batteries lithium-ion à l'état solide WO2021189083A1 (fr)

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EP21770847.8A EP4122032A1 (fr) 2020-03-18 2021-03-18 Anode à base de métal lithium à haute densité d'énergie pour batteries lithium-ion à l'état solide
CN202180022486.7A CN115315832A (zh) 2020-03-18 2021-03-18 用于固态锂离子电池的高能量密度锂金属基阳极
CA3171696A CA3171696A1 (fr) 2020-03-18 2021-03-18 Anode a base de metal lithium a haute densite d'energie pour batteries lithium-ion a l'etat solide
MX2022011419A MX2022011419A (es) 2020-03-18 2021-03-18 Ánodo a base de metal de litio de alta densidad energetica para baterías de iones de litio de estado sólido.
KR1020227035613A KR20220156571A (ko) 2020-03-18 2021-03-18 고체 상태 리튬 이온 배터리를 위한 고에너지밀도 리튬 금속 기반 애노드
JP2022555782A JP2023518060A (ja) 2020-03-18 2021-03-18 固体リチウムイオン電池用の高エネルギー密度リチウム金属系負極

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